Novel epoxide derivatives of allylarylphenols

ABSTRACT

The present invention relates to novel epoxides having the formulas  
                 
 
     where Y is a CO, CO 2  or SO 2 , AR is the same or different divalent unsubstituted or substituted aromatic, halogen-substituted aromatic or cyano-substituted aromatic hydrocarbon radical having from 6 to 20 carbon atoms, Z is a divalent hydrocarbon or ether radical having from 1 to 20 carbon atoms, including Y—Z—Y being CO, and R* is an alkyl, aryl, arylalkyl, alkoxy, aryloxy or arylalkoxy radical having from 0-20 carbon atoms. The epoxides of the present invention are useful in the formation of epoxy resins.

BACKGROUND OF THE INVENTION

[0001] The epoxy intermediates and resins industry (Encyclopedia ofChemical Technology, Volume 9. Fourth Edition. John Wiley & Sons Page730) is a multibillion dollar business that is based on the followingtechnology that involves no less than ten chemical reactions. Thisapplication is a continuation-in-part of Ser. No. 60/284,325 filed Apr.17, 2001.

[0002] Benzene+propylene→isopropylbenzene

[0003] Isopropylbenzene→cumene hydroperoxide

[0004] Cumene hydroperoxide→phenol+acetone.

[0005] Phenol+acetone→“Bis-A” or Phenol+formaldehyde→“Bis-F”

[0006] Propylene+chlorine→allyl chloride

[0007] Allyl chloride+sodium hydroxide+chlorine→propylene chlorohydrins

[0008] Propylene chlorohydrins+sodium hydroxide→epichlorohydrin

[0009] Bis-A+epichlorohydrin+NaOH→“Bis-A glycidol ether”

[0010] Bis-A glycidol ether+Bis-A→epoxy resin

[0011] Sodium chloride+water→chlorine+sodium hydroxide.

[0012] Several aspects of the above reaction sequence have negativeprocess implications with regards to yields, chlorinated byproducts,hydraulic load and biological hazards. These include but are not limitedto the following: (a) benzene is a known carcinogen, (b) Bis-A is anendocrine disrupter (mimics estrogen), (c) chlorination of propylene toallyl chloride (step 5) and the addition of hypochlorous acid (step 6)yield higher chlorinated byproducts resulting in ˜⅓ pounds ofchlorinated waste per pound of epichlorohydrin. In addition, the processrequires a chlor-alkali facility, hence a local source of salt and hugevolumes of water. The products and processes of the present inventionameliorate if not eliminate some of the disadvantages of prior art epoxyproducts and processes.

BRIEF DESCRIPTION OF THE INVENTION

[0013] The present invention relates to the preparation of bis-estersand ethers of allylarylphenols and the epoxidation of the allyl moietyto provide novel bis-epoxide ester and ether intermediates useful in thepreparation of epoxy resins. The epoxy ethers and esters of carboxylic,carbonic, phosphoric and sulfonic acids of the present invention arerepresented by the following formulas:

[0014] where Y is a CO, CO₂ or SO₂, AR is a divalent unsubstituted orsubstituted aromatic, halogen-substituted aromatic or cyano-substitutedaromatic hydrocarbon radical having from 6 to 20 carbon atoms, Z is adivalent hydrocarbon or ether radical having from 1 to 20 carbon atoms,including YZY being CO, and R* is an alkyl, aryl, arylalkyl, alkoxy,aryloxy or arylalkoxy radical having from 0-20 carbon atoms.

[0015] Preferred aromatic “AR” radicals include divalent benzene,naphthalene, toluene, chlorobenzene, cyanobenzene, xylene andethylbenzene radicals. Preferred hydrocarbon “Z” radicals includedivalent aliphatic radicals such as divalent methane, ethane, butane,and cyclohexane, divalent aromatic radicals such as divalent benzene,toluene, xylene and ethylbenzene radicals. Preferred ether “Z” radicalsinclude such divalent radicals as divalent ethoxyethane, ethoxypropane,propoxypropane, butoxyethane methoxybenzene, and ethoxybenzene.Preferred R* radicals include methyl, ethyl, propyl, isobutyl,cyclohexyl, phenyl, benzyl, naphthyl, toluyl and xylyl.

DETAILED DESCRIPTION OF THE INVENTION

[0016] The preparation of allylarylphenols used in the present inventionis well documented in the chemical literature and is illustrated for2-allylphenol. The formation of the ether and the rearrangement arecarried out in the same reactor.

C₆H₅OH+CH₂═CHCH₂X+base→C₆H₅₀CH₂CH═CH₂+HX,

[0017] where X is Cl, Br, acetate, tosylate, or similar leaving group.

C₆H₅OCH₂CH═CH₂ ⁺→2-CH₂═CHCH₂C₆H₄OH

[0018] The preparation of bis-aromatic disulfonyl chlorides is alsowell-documented in the literature and is achieved via the sulfonation orchlorosulfonation of aromatic compounds (“Friedel Crafts and RelatedReactions”, Volume 3, Part 2, page 1355, Interscience Publishers, 1964,C. M. Suter, “Organic Chemistry of Sulfur Compounds”, Chapter 3 JohnWiley and Sons, 1944, and “Organic Functional Group Preparations”, S. R.Sandler and W. Karo, Academic Press 1968, page 506). The reactions arepreferably carried out in 1,2-dichloroethane as solvent. If higherreaction temperatures are required for the bis sulfonation, the reactionmay be performed without a solvent. Reaction of the aromatic disulfonylchloride with two equivalents of the allylarylphenol in the presence ofan acid acceptor gives the desired bis-sulfonate ester which isconverted to the desired bis-epoxide in essentially quantitative yieldwith standard utilized oxidants e.g., peracetic acid, 3-chloroperbenzoicacid, hydrogen peroxide, t-butyl hydroperoxide etc. The latter tworeagents require a metal catalyst (“Oxidations in Organic Chemistry”, M.Hudlicky, ACS Monograph 186, page 60. American Chemical Society).

[0019] The allylarylphenyl ester of dicarboxylic acids are convenientlyprepared from the reaction of the dicarboxylic acid dichloride with theallylarylphenol in an inert solvent such as toluene, dichloromethane,1,2-dichloromethane etc. in the presence of a hydrogen acceptor such aspyridine, triethylamine, etc. The use of the hydrogen acceptor can beeliminated by simply refluxing the phenol and acid chloride in a higherboiling solvent to effect displacement of the anhydrous HCl that may berecovered for alternate uses. If a lower dialkyl ester of thedicarboxylic acid is available, ester exchange of the allylarylphenol inthe presence of a transesterification catalyst can serve as analternative route to the bis-aryl ester (“Encyclopedia of ChemicalTechnology”, Volume 9. Fourth Edition, John Wiley & Sons, page 755,“Survey of Synthesis”, Calvin Buehler and D. E Pearson, WileyInterscience 1970, page 101 and “Preparation of Esters usingPolyphosphate Ester”, J. H. Adams, J. G. Paul and J. R. Lewis,Synthesis, 429-30, 1979). The oxidation methods are identical asdescribed above for the sulfate esters.

[0020] In the manner described for the preparation of allylphenyl estersfrom dicarboxylic acid dichlorides, the allylphenyl esters of dicarbonicacids are prepared from the corresponding bis-chloroformates with twoequivalents of allylphenol. Similarly a carbonic acid ester, is preparedfrom two equivalents of allylphenol and phosgene.

[0021] The allylaryl esters of the phosphoric and phosphonic acids arereadily prepared from the acid dichlorides since phosphorus oxychloride,POCl₃, is the basic phosphorus precursor (“Organophosphorus Compounds”,G. M. Kosolapoff, John Wiley, 1950). Thus, utilization of an inertsolvent and an acid acceptor as described above for the carboxylic acidsgives high yields of the desired allylaryl esters that are then oxidizedto the bis-epoxides as described above.

[0022] The allylaryl ethers are prepared by displacement reactions ofthe desired dichloride with either the allylaryl phenoxide anion ordisplacement by the 2,3-epoxypropylphenoxide anion. For substrates thatrequire higher temperatures to carry out the displacement such as4-chliorophenyl sulfone, the preferred anion is the2,3-epoxypropylphenoxide. With the allylaryl phenoxide, displacementoccurs but the 2,3-olefinic bond undergoes thermal isomerization to the1,2-olefin. With the more reactive olefins, such as 1,4-dichlorobutaneand 3,6-dichloropyridazine, olefin isomerization is not a problem. Forunreactive aryl halides, reaction conditions for the Ullman reactionether synthesis is required. Within the scope of the present invention,optimum reaction conditions can be obtained in a routine manner.

[0023] The following are examples of allylarylphenols that may bereacted with either derivatives of organic acids or dihalo compounds toform the compounds of this invention: 2-allylphenol,2-allyl-6-methylphenol, 4-allyl-2,6-dimethylphenol,2-allyl-4-dodecylphenol, 2-allyl-4-methoxyphenol,2-allyl-4-phenoxyphenol, 2-allyl-4-cyclohexylphenol, 3-allyl-4-hydroxyethyl benzoate, 2-allyl-4-chlorophenol, 2-allyl-4-cyanophenol,2-allyl-4-benzylphenol, 2-allyl-4-chloromethylphenol,1-allyl-2-naphthol, and 2-allyl-4-phenylphenol.

[0024] The following are examples of the disulfonic acid compounds thatcan be employed to prepare the diepoxides of the present invention:benzene-1,3-disulfonyl chloride, naphalene-2,6-disulfonyl chloride,phenyl ether-1,4-disulfonyl chloride, 4,4*biphenyldisulfonyl chloride,2,5-dirnethylbenzene-1,3-disulfonyl chloride,4-octylbenzene-1,3-disulfonyl chloride, 4-methoxybenzene-1,3-disulfonylchloride, 4-chlorobenzene-1,3-disulfonyl chloride,4-carboethoxy-1,3-disulfonyl chloride 3,5-pyridinedisulfonyl chloride,3,5-pyridine-N-oxide disulfonyl chloride, and 2,5-thiophenedisulfonylchloride.

[0025] The following are examples of the dicarboxylic acid compoundswhich can be employed in the preparation of the novel epoxides of thepresent invention: terephtholyl chloride, iso-phtholyl chloride,succinoyl choride, adipoyl chloride, 1,4-cyclohexane carboxylic aciddichloride, dimethyl terephthalate, diethyl succinate,4,4*-biphenyldicarboxylic acid dichloride, malonyl chlorde, oxaloyl chloride and3,5-pyridine-dicarboxylic acid dichloride.

[0026] The following are examples of the starting materials which can beemployed in the formation of the novel bis-epoxide ethers of the presentinvention: 1,2-dichloroethane, 1,4-dichlorobutane,1,4-dichloro-2-butene, 1,12-dichlorododecane, 1,4-dichlorocyclohexane,4-chlorophenyl sulfone, 4-(2-chloroethoxyphenyl)sulfone,4,4*-dichlorobenzophenone, 2,6-difluorobenzonitrile,2,4-dichloroacetophenone, 2,4-dichlorotoluene, 2,4-dichloro-1-methylnaphthoate, 2,6-dichloropyridine-N oxide and chlorinated polyethyleneglycols having the formula ClCH₂CH₂(OCH₂CH₂)_(x)Cl where x is a numberfrom 1 to 10.

[0027] The condensation of the bis-epoxides of this invention withdiphenols, e.g., bisphenol-A, bisphenol-F, 4-hydroxyphenyl sulfone,4,4*-dihydroxybenzophenone, 4,4*-dihydroxybiphenyl and1,4-(4-hydroxyphenyl)butane, with dicarboxylic acids, e.g., isophthalicacid, succinic acid and cyclohexane dicarboxylic acid, withaminophenols, e.g., 4-aminophenol, 4-amino-4*-hydroxyphenyl ether, and4-amino-4*-hydroxybiphenyl, with hydroxy carboxylic acids, e.g.,4-hydroxybenzoic acid and 6-hydroxy-6-hydroxy-2-naphthoic acid, withamino acids, e.g., 4-aminobenzoic acid, and 4-aminophenoxybenzoic acid,with diamines, e.g., 4,4*-diaminophenyl ether 1,3-diamonobenzene and1,3-diamonipropane or with disulfonamides, e.g., 1,3-benzenedisulfoniceacid:bis-N-methyl amide results in new and valuable epoxy resins forprotective coatings, structural composites, electrical laminates andadhesives. The chemistry provides the opportunity to manufacture resinswith fewer chemical transformations, less capital and a reduction in thewaste load associated with the Bis-A/epichlorohydrin technology. Theresins can be obtained from the bis-epoxides using condensationprocedures established in the art. An example of a resin synthesis fromreadily available starting materials using the epoxide route of thepresent invention that requires only six chemical transformation isoutlined below:

[0028] 1. toluene→phenol (T. Shikada et al, J. Chem. Soc., Chem.Commun., 1994)

[0029] 2. propylene→allyl acetate

[0030] 3. phenol+allyl acetate→2-allylphenol

[0031] 4. 2-allylphenol +isophthalic acid→diester

[0032] 5. diester+H₂O₂→diepoxide

[0033] 6. diepoxide+succinic acid→epoxy resin

[0034] The following examples further illustrate novel epoxides of thepresent invention:

EXAMPLE 1

[0035] Preparation of 2,5-Dimethyl-1,3-Benzenedisulfonic Acid:BIS-[2-(2,3-Epoxypropyl)]Phenyl Ester.

[0036] 1,4-Dimethylbenzene (10.6 g, 0.1 mol) was added dropwise tochlorosulfonic acid (60 g, 0.51 mol ) at room temperature with stirring.After the addition was complete, the reaction mixture was heated to˜100C for 1 hr, cooled to room temperature and poured ontoice-water-1,2-dichloromethane mixture with stirring. The organic layerwas separated, washed with water (2×), dried over anhydrous MgSO₄ andthe solvent evaporated to give 2,5-dimethyl-1,3-benzenedisulfonylchloride, 26 g (86%) as a viscous liquid that solidified on standing, mp24-27° C. Reported 25-27C. (C. M. Suter, Organic Chemistry of SulfurCompounds, Chapter 3).

[0037] The disulfonyl chloride (20 g, 0.066 mol) and 2-allylphenol(17.70 g, 0.132 mol) were diluted with toluene (200 ml) and added to a500 ml 3-necked round bottom flask equipped with a magnetic stirrer,condenser, and thermometer. Triethylamine (17 ml, 0.132 mol) was addeddropwise and the mixture was stirred and refluxed for 2 hr. Aftercooling, the precipitated triethylamine hydrochloride was removed byfiltration and the toluene evaporated in vacuo to give 30.2 g (94%) ofthe desired 2,5-dimethyl-1,3-benzenedisulfonic acid bis-(2-allylphenylester). Recrystallization from ethyl acetate-methanol gave product mp76-78° C. MS m/z 498 (M+ calcd for C₂₆H₂₆O₆S₂=498). H NMR (300 MHz,CDCl₃) d 2.44 (s, 3, CH₃), 3.40-3.50 (m, 4, CH₂), 5.03-5.13 (m, 4, CH₂vinyl), 5.81-6.00 (m, 2, CH vinyl), 6.88 (d, 2, aromatic), 7.09-7.37 (m,6, aromatic), 8.09 (s, 2, aromatic).

[0038] The above diolefin (2.0 g) was dissolved in dichloromethane alongwith m-chloroperbenzoic acid (3.0 g, ˜70%) and the solution stirredovernight at room temperature to form the diepoxide. The dichloromethanesolution was washed with aqueous Na₂CO₃, aqueous Na₂SO₃ and water, driedover anhydrous MgSO₄ and the solvent evaporated. Recrystallization frommethanol gave product mp 90-92C. Utilization of peracetic acid for 72 hrgave identical results. H NMR (300 MHz, CDCl₃). d 2.44 (s ,3, CH₃),2.60-2.73 (m, 2, CH₂ epoxypropyl), 2.73-2.99 (m, 4, CH₂ epoxypropyl),3.06-3.15 (m, 2, CH₂ epoxypropyl), 3.16-3.25 (m, 2, CH epoxypropyl),3.25 (s, 3, CH₃), 6.79 (d, 2, aromatic), 7.09-7.37 (m, 6, aromatic),8.09 (s, 2, aromatic).

EXAMPLE 2

[0039] Preparation of 1,3-Benzenedisulfonic Acid:Bis-[2-(2,3-Epoxypropyl)]Phenyl Ester

[0040] The diolefinic precursor, 1,3-benzenedisulfonic acidbis-(2-allyl) phenyl ester, was prepared from 1,3-benzenedisulfonylchloride and 2-allylphenol as described in Example 1. The product was aviscous liquid. MS m/z 470 (M+ calcd for C₂₄H₂₂O₆S₂=470). H NMR (300MHz, CDCl₃) d 3.22-3.28 (d, 4, CH₂), 4.94-5.09 (m, 4, CH₂ vinyl),5.68-5.91 (m, 4, CH vinyl), 6.97-7.03 (d, 2, aromatic), 7.12-7.25 (m, 6,aromatic), 7.72-8.82 (m, 4, aromatic).

[0041] Epoxidation of the above diolefin with 3-chloroperbenzoic acidusing the procedures of Example 1 gave the desired diepoxide as aviscous oil. H NMR (300 MHz, CDCl₃) d 2.48-2.51 (m, 2, CH₂ epoxypropyl),2.66-2.79 (m, 4, CH₂ epoxypropyl), 2.87-3.00 (m, 2, CH₂ epoxypropyl),3.10-3.16 (m, 2, CH epoxypropyl), 6.91-6.98 (m, 2, aromatic), 7.14-7.27(m, 4, aromatic), 7.62-7.69 (m, 2, aromatic), 7.88-8.25 (m, 4,aromatic).

EXAMPLE 3

[0042] Preparation of 4,4-Biphenyldisulfonic Acid:Bis-[2-(2,3-epoxypropyl)]Phenyl ester.

[0043] The diolefinic precursor, 4,4-biphenyldisulfonic acid:bis-(2-allyl) phenyl ester, was prepared from 4,4-biphenyl disulfonylchloride and 2-allylphenol as described in Example 1. Recrystallizationfrom methanol gave product, mp 88-900 C. Reported 88-900 C (C. M. Suter,Organic Chemistry of Sulfur Compounds, Chapter 3).MS m/z 548 (MHz calcdfor C₃₀H₂₈O₆S₂=548). H NMR (300 MHz, CDCl₃) d 2.27 (d, 2, CH₂),4.96-5.06 (m, 2, CH₂ vinyl), 5.72-5.91 (m, 1, CH vinyl), 7.06-7.34 (m,4, aromatic), 7.94 (q, 4, aromatic).

[0044] Epoxidation of the above diolefin with 3-chloroperbenzoic acidgave the desired diepoxide. Recrystallization from methanol gave productmp 99-101° C. H NMR (300 MHz, CDCl₃) d 2.24 (m, 2, CH₂ epoxypropyl),2.66-2.91 (m, 6 CH₂ epoxypropyl), 3.06-3.16 (m, 2, CH epoxypropyl), 7.01(m, 1, aromatic), 7.16-7.28 (m, 2, aromatic), 7.40-7.47 (m, 1,aromatic), 7.91 (q, 4, aromatic).

EXAMPLE 4

[0045] Preparation of 4,4-Phenyl Ether Disulfonic Acid:Bis-[2-(2,3-Epoxypropyl)]Phenyl Ester.

[0046] The diolefinic precursor, 4,4-phenyl ether disulfonic acid:bis(2-allyl) phenyl ester, was prepared from 4,4-phenyl ether disulfonylchloride and 2-allylphenol as described in Example 1. The diolefin was aviscous oil. MS m/z 564 (M+ calcd for C₃₀H₂₆O7S₂=564). H NMR (300 MHz,CDCl₃) d 3.18-3.27 (m, 2, CH₂), 5.00-5.18 (m, 2, CH₂ vinyl), 5.78-5.94(m, 1, CH vinyl), 7.06-7.59 (m, 4, aromatic), 7.66 (q, 4 aromatic).

[0047] Epoxidation of the above diolefin with 3-chloroperbenzoic acidgave the desired diepoxide as a viscous oil. H NMR (300 MHz, CDCl₃) d2.56-2.60 (m, 2, CH₂ epoxypropyl), 2.66-2.91 (m, 6, CH₂ epoxypropyl),3.06-3.15 (m, 2, CH epoxypropyl), 7.07-7.69 (m, 4, aromatic), 7.66 (q,4, aromatic).

EXAMPLE 5

[0048] Preparation of 2,6-Napthalenedisulfonic Acid:Bis-[2-(2,3-Epoxypropyl)]Phenyl Ester.

[0049] The diolefinic precursor, 2,6-napthalenedisulfonicacid-bis-(2-allyl) phenyl ester was prepared from2,6-napthalenedisulfonyl dichloride as described in Example 1. Thediolefin, after recrystallization from hexane-dichloromethane, had mp138-141° C. MS m/z 520 (m+ cacld for C₂₈H₂₄O₆ S₂=520). H NMR (300 MHz,CDCl₃) d 3.29 (d, 2, CH₂), 4.94-5.03 (m, 2, CH₂ vinyl), 5,69-5.88 (m, 1,CH vinyl), 7.04-7.23 (m, 4, aromatic), 8.07-8.43 (m, 3, aromatic).

[0050] Epoxidation of the diolefin with 3-chloroperbenzoic acid gave thedesired diepoxide. After recrystallization from methanol, the producthad mp 135-137° C. H NMR (300 MHz, CDCl₃) d 2.48-2.51 (m, 2, CH₂epoxypropyl), 2.66-2.79 (m, 2, CH₂ epoxypropyl), 2.81-2.90 (m, 4, CH₂epoxypropyl, 3.09-3.21 (m, 2, CH epoxypropyl), 7.09-7.46 (m, 6,aromatic), 8.06-8.37(m, 6, aromatic).

EXAMPLE 6

[0051] Preparation of Bis 1,4-[2-(2,3-Epoxypropyl)Phenoxy]Butane

[0052] Powdered sodium hydroxide (4.0 g, 0.1 mol) was dissolved withheating ˜50C in dimethyl sulfoxide (50 ml). 2-Allylphenol (13.4 g, 0.1mol) was added to the dimethyl sulfoxide solution followed by the1,4-dichlorobutane (6.35 g, 0.05 mol) and the mixture was heated to 80Cfor 5 hr. After cooling, the reaction mixture was diluted with water andthe product isolated by extraction with 1,2-dichloromethane. Filtrationthrough a small amount of silica gel and evaporation of solvent in vacuogave 13.1 g (82%) of a colorless oil, bis-1,4-(2-allylphenoxy) butanethat crystallized on standing, mp 38-40C. MS m/z 322 (M+cacld forC₂₂H₂₆O₂=322). H MNR (300 MHz, CDCl₃) d 2.08 (d, 2, CH₂), 3.50 (d, 2,CH₂), 4.07-4.21 (m, 2, OCH₂), 5.03-5.14 (m, 2, CH₂ vinyl), 6.00-6.15 (m,1, vinyl CH), 6.90-7.03 (m, 2, aromatic), 7.20-7.30 (m, 2, aromatic).The diolefin (2.0 g, 0.0062 mol) was added to a dichloromethane solutionof 3-chloroperbenzoic acid (5.0 g, ˜70% active, 50 ml) that was predriedover anhydrous MgSO₄. The reaction mixture was stirred overnight at roomtemperature, washed with dilute aqueous sodium sulfite and diluteaqueous sodium carbonate, dried over anhydrous Mg SO₄ and the solventevaporated in vacuo to give ˜2.0 g of the diepoxide as a viscous oil. MSm/z 354 (M+ calcd for C₂₂H₂₆O₄=354). H NMR (300 MHz, CDCl₃) d 2.08 (d,2, CH₂), 2.57 (d, 1, epoxypropyl CH₂), 2.72-2.83 (m, 2, CH₂epoxypropyl), 2.83-3.03 (m, 2, epoxypropyl), 3.17-3.28 (m, 1, CHepoxypropyl), 6.78-7.04 (m, 1, aromatic), 7.20-7.35 (m, 2, aromatic).

EXAMPLE 7

[0053] Preparation of Bis-1,2-[2-(2,3-Epoxypropyl)Phenoxy]Ethane

[0054] Bis-1,2-(2-allylphenoxy)ethane was prepared from 2-allylphenoland 1,2-dichloroethane as described in Example 6 with the followingexception. The crude product was distilled in vacuo to remove unreacted2-allylphenol and the monosubstituted product prior to filtrationthrough silica gel to give a viscous oil. MS m/z 294 (M+ calcd forC₂OH₂₂O₂=294). H NMR (300 MHz, CDCl₃) d 3.40-3.50 (d, 2, CH₂), 4.40 (s,2, OCH₂), 5.05-5.14 (m, 2, CH₂ vinyl), 5.90-6.08 (n, 1, CH vinyl),6.91-7.09 (m, 2, aromatic), 7.18-7.32(m, 2, aromatic).

[0055] Oxidation as described in Example 6 gave the desired diepoxide asa viscous oil. MS m/z 326 (M+calcd for C₂₀H₂₂O₄=326). H NMR (300 MHz,CDCl₃) d 2.57 (d, 1, CH₂ epoxypropyl), 2.64-3.00 (m, 3, CH₂epoxypropyl), 3.14-3.30 (m, 2, CH epoxypropyl), 4.40 (s, 2, OCH₂),6.89-7.02 (m, 2, aromatic), 7.70-7.55 (m, 2,aromatic).

EXAMPLE 8

[0056] Preparation of Bis-[2-(2,3-Epoxypropyl)Phenyl]Phenyl Phosphate

[0057] Phenyl dichlorophosphate (10.5 g, 0.05 mol) was added dropwise toa solution of 2-allylphenol (13.4 g, 0.1 mol) and triethylamine (13.9ml, 0.1 mol) in 1,2-dichloroethane (200 ml) and the mixture refluxed for2 hr. After cooling, the precipitate, triethylamine hydrochloride wasfiltered, and the organic solution washed with water, dried overanhydrous Mg SO₄ and evaporated in vacuo. The unreacted 2-allylphenolwas removed by vacuum distillation to give bis-[2-allylphenyl) phenylphosphate as a viscous liquid. MS m/z 406 (M+calcd for C₂₄H₂₃O₄P=406). HNMR (300 MHZ, CDCl₃) d 3.46 (d, 4 CH₂), 4.95-5.15 (m, 4 CH₂ vinyl),5.82-6.00 (m, 2 CH vinyl), 7.20-7.50 (m, 13, aromatic).

[0058] The above diolefin was converted to the desired diepoxide asdescribed in Example 6. H NMR (300 MHz, CDCl₃) d 2.46 (d, 2, CH₂epoxypropyl), 2.62-2.90 (m, 6, CH₂ epoxypropyl), 3.03-3.11 (m, 2, CHepoxypropyl), 7.21-7.51 (m, 13, aromatic).

EXAMPLE 9

[0059] Preparation of Isophthalic Acid: BIS-[2-(2,3-Epoxypropyl)PhenylEster]

[0060] Isophthaloyl dichloride (3.19 g, 0.0157 mol) and 2-allylphenol(4.21, 0.0313 mol) were diluted with dichloromethane (50 ml) andtriethylamine (3.16 g, 0.0313 mol) added dropwise at room temperature.After stirring for 3 hr at room temperature, the amine hydrochloride wasremoved by filtration and the organic solution washed with water anddried over anhydrous Mg SO₄. Evaporation of the solvent in vacuo gavethe bis-allylphenyl isophthalate as a colorless oil. MS m/z 398 (M+calcd for C₂₆H₂₂O₄=398). H NMR (300 MHz, CDCl₃) d 3.46 (d, 2, CH₂),5.01-5.12 (m, 2, CH₂ vinyl), 5.90-6.05 (m, 1, CH vinyl), 7.20-7.40 (m,4, aromatic), 7.65-7.77 (m, 1, aromatic), 8.25-8.33(m, 1, aromatic),9.05 (s, 1, aromatic).

[0061] The above diolefin was converted to the desired diepoxide asdescribed in Example 6. H NMR (300 MHz, CDCl₃) d 2.5 (d, 1, CH₂epoxypropyl), 2.62-2.96 (m, 3, CH₂ epoxypropyl), 3.22-3.30 (m, 1, CHepoxypropyl), 7.15-7.47 (m, 4, aromatic) 7.83-7.91(m, 1, aromatic),8.25-8.33 (m, 1, aromatic), 9.05 (s, 1, aromatic).

EXAMPLE 10

[0062] Preparation of 3,6-Bis-[2-(2,3-Epoxypropyl)Phenoxy]Pyridazine

[0063] 2-Allylphenol (10 g, 0.075 mol) was added to a solution ofperacetic acid (30 g, 30% active) in dichloromethane (100 ml) that hadbeen dried over anhydrous MgSO₄. The reaction mixture was stirred atroom temperature for 48 hrs. The dichloromethane solution was washedwith water, dilute aqueous NaCO₃, dilute aqueous NaSO₃ and dried overanhydrous MgSO₄. After evaporation of the solvent in vacuo,2-(2,3-epoxypropyl)phenol was isolated as viscous liquid. MS m/z 150(M+calcd for C₉H₁₀O₂150). H NMR (300 MHz, CDCL₃) d 2.65-2.80(m, 2, CH₂epoxypropyl), 2.87-2.93 (m, 1, CH₂ epoxypropyl), 3.10-3.21 (m, 1, CH₂epoxypropyl), 3.50-3.60 (m, 1, CH epoxypropyl), 6.80-7.25 (m, 4,aromatic). 2-(2,3-Epoxypropyl)phenol (0.9 g, 0.006 mol) was added to asolution of powdered sodium hydroxide (0.24 g, 0.006 mol) indimethylacetamide(30 ml) and the solution heated at 80C for 1 hr. Thereaction mixture was diluted with water and extracted withdichloromethane, dried over anhydrous MgSO₄ and evaporated in vacuo togive a solid that on recrystallization from methanol gave product mp150-152C. MS m/z 376 (M+ cacld for C₂₂H₂₀N₂O₄=376). H NMR (300 MHz,CDCl₃) d 3.62 (dq, 2, CH₂ epoxypropyl), 4.57 (dq, 2, CH₂ epoxypropyl),5.15-5.32 (m, 1, CH epoxypropyl), 6.78-6.93 (m, 2, aromatic), 7.11 (s,1, heteroaromatic), 7.15-7.28(m, 2, aromatic).

EXAMPLE 11

[0064] Preparation of 4-[2-(2,3-Epoxypropyl)Phenyl]Sulfone

[0065] This compound was prepared using dichlorophenyl sulfone and2-allylphenol as described in Example 10. The compound is a viscousliquid and was purified by column chromatography utilizing silica gel. HNMR (300 MHz ,_(CDCL3)) d 3.35 (dq, 2, CH₂ epoxypropyl), 3.91(dq, 2, CH₂epoxypropyl), 5.03-5.20 (m, 1, CH epoxypropyl), 6.84-7.03 (m, 2,aromatic), 7.22-7.35 (m, 2, aromatic), 7.75 (d, 2, aromatic).

[0066] The preparation of epoxy resins from the described epoxides ofthe present invention follows procedures described in the literature forthe preparation of epoxy resins.

What is claimed is:
 1. Diepoxide esters and ethers of allyl phenolshaving the formulas:

where Y is a CO, CO₂ or SO₂, AR is the same or different divalentunsubstituted or substituted aromatic, halogen-substituted aromatic orcyano-substituted aromatic hydrocarbon radical having from 6 to 20carbon atoms, Z is a divalent hydrocarbon or ether radical having from 1to 20 carbon atoms, including Y-Z-Y being CO, and R* is an alkyl, aryl,arylalkyl, alkoxy, aryloxy or arylalkoxy radical having from 0-20 carbonatoms.
 2. The diepoxide esters of claim 1 having the formula:

where AR* is a divalent aromatic radical of 6 to 20 carbon atoms.
 3. Thediepoxide esters of claim 1 having the formula:

where X is arylene, alkylene or arylalkylene or alkylarylene.
 4. Thediepoxide esters of claim 1 having the formula


5. The bis-epoxides ethers of claim 1 having the formula:

where X is arylene, alkylene, alkylarylene or arylalkylene.
 6. Thediepoxide ester of claim 1 having the formula

where X is arylene, alkylene, alkylarylene or arylalkylene.
 7. Thediepoxide of claim 1 having the formula


8. The diepoxide of claim 6 where the bis-carbonate isresorcinol:bis[2(2.3-epoxypropyl)phenyl]carbonate.
 9. The diepoxide ofclaim 7 where the bis-carbonate isbis[2(2,3-epoxypropyl)phenyl]carbonate.
 10. The diepoxide of claim 2where the diester is 2,5-dimethyl-1,3-benzenedisulfonic disulfonic acid:bis-[2-(2,3-epoxypropyl)]phenyl ester.
 11. The diepoxide of claim 2where the diester is 1,3-benzenedisulfonic acidbis-[2-(2,3-epoxypropyl)]phenyl ester.
 12. The compound of claim 2 wherethe diester is 4,4-biphenyldisulfonic acidbis-[2(2,3-epoxypropyl)]phenyl ester.
 13. The diepoxide of claim 2 wherethe diester is 4,4-phenyl ether disulfonic acid:bis-[2-(2,3-epoxypropyl)]phenyl ester.
 14. The diepoxide of claim 2where the diester is 2,6-napthalenedisulfonic acid:bis-[2-(2,3-epoxypropyl)]phenyl ester.
 15. The diepoxide of claim 3where the diester is isophthalic acid: bis-[2-(2,3-epoxypropyl)]phenylester.
 16. The diepoxide of claim 3 where the diester is succinic acid:bis-[2-2,3-epoxypropyl)]phenyl ester.
 17. The diepoxide of claim 4 wherethe diester is bis-[2-(2,3-epoxypropyl)phenyl]phenyl phosphate.
 18. Thediepoxide of claim 5 where the diether isbis-[2-(2,3-epoxypropyl)phenoxy]ethane.
 19. The diepoxide of claim 5where the ether is bis-[2-(2,3-epoxypropyl)phenoxy]butane.
 20. Thediepoxide of claim 5 where the ether isbis-[2-(2,3-epoxypropyl)phenoxy]pyridazine.
 21. The diepoxide of claim 5where the ether is 4-[2-(2,3-epoxypropyl)phenyl]sulfone.
 22. Thepreparation of bis-epoxides of aryl sulfate esters of claim 2 byreacting an aryl disulfonic acid compound with an allyl compound of theformula CH₂═CH—AR wherein AR is an aromatic moiety and epoxidizing theresulting diolefin.
 23. The preparation of bis-epoxides of carboxylicacids esters of claim 3 by reacting a dicarboxylic acid compound with anallyl compound of the formula CH₂═CH—CH₂—AR wherein AR is an aromaticmoiety and epoxidizing the resulting diolefin.
 24. The preparation ofbis-epoxides of phosphorus containing esters of claim 4 by reacting aphosphonic acid with an allyl compound of the formula CH₂═CH—CH₂—ARwherein AR is an aromatic moiety and epoxidizing the resulting diolefin.25 The preparation of bis-epoxides of ethers of claim 5 by reacting adihalo hydrocarbon with an allyl compound of the formula CH₂═CH—CH₂—ARwherein AR is an aromatic moiety and epoxidizing the resulting diolefin.26. The preparation of diepoxides of claim 6 which comprises reacting abis -chloroformate with an allyl compound of the formula CH₂═CH—CH₂—ARand epoxidizing the resulting diolefin.
 27. The preparation ofdiepoxides of claim 7 comprising reacting phosgene and an allyl compoundof the formula CH₂═CH—CH₂—AR and epoxidizing the resulting diolefin.